Conversion of alkyl and aryl hydroxy compounds producing aldehyde, alcohol and ketone using manganese oxide/nickel oxide/magnesium oxide catalysts

ABSTRACT

Alkyl and aryl hydroxy compounds are converted to aldehydes, alcohols, and ketones in the presence of hydrogen using a catalyst comprised of the oxides of manganese, nickel and magnesium.

BRIEF SUMMARY OF THE INVENTION

Alkyl and aryl hydroxy compounds are subjected to elevated temperatureand hydrogen in the presence of a catalyst comprising manganeseoxide/nickel oxide/magnesium oxide. Aliphatic alcohols are converted toaldehyde and ketone. Aromatic hydroxy compounds are converted tocycloaliphatic alcohol and ketone.

DETAILED DESCRIPTION

This invention relates to the conversion of alkyl and aryl hydroxycompounds. In one of its aspects, the invention relates to theconversion of an alkyl and/or an aryl hydroxy compound to at least oneof an aldehyde, alcohol and ketone under dehydrogenation conditions. Inanother of its aspects, the invention relates to the production ofuseful compounds employing a catalyst essentially comprising manganeseoxide, nickel oxide and magnesium oxide.

In one of its concepts the invention provides a method for converting analkyl and/or an aryl hydroxy compound under dehydrogenation conditionsto produce usable compounds, e.g., an aldehyde, alcohol, and/or ketoneemploying a catalyst essentially comprising manganese oxide, nickeloxide, and magnesium oxide. In another of its concepts, the inventionprovides a method for converting an aliphatic alcohol to an aliphaticaldehyde and/or ketone by subjecting the same to dehydrogenationconditions in the presence of a catalyst that is herein described. Inanother of its concepts, the invention provides a process for theconversion of an aromatic hydroxy compound to at least one of acycloaliphatic alcohol and a cycloaliphatic ketone by subjecting thesame in the presence of hydrogen to the action of a catalyst as hereindescribed. In a more specific concept of the invention, it provides amethod for preparing an aliphatic aldehyde from a primary aliphaticalcohol subjecting the same under dehydrogenation conditions to theaction of a catalyst as herein described. Further, in another concept ofthe invention it provides a process for converting an aliphaticsecondary alcohol to an aliphatic ketone by subjecting said alcohol todehydrogenation conditions employing a catalyst as herein described.Still, in a further concept of the invention, it provides a method forpreparing a cycloaliphatic alcohol from an aromatic hydroxy compound bysubjecting the same to dehydrogenation conditions in the presence of acatalyst as herein described. Further, still, in another concept of theinvention it provides a method of preparing a cycloaliphatic ketone froman aromatic hydroxy compound.

Aldehydes, alcohols and ketones have a wide range of applications thatinclude solvents, additives and intermediates in the preparation ofpolymers such as nylon, dyes, surfactants, pharmaceuticals, and rubberchemicals. Some of the more widely known materials are methyl ethylketone, prepared by dehydrogenation or oxidation of 2-butanol;cyclohexanone, prepared by the dehydrogenation of cyclohexanol or airoxidation of cyclohexane; and cyclohexanol, prepared by thehydrogenation of aryl hydroxy compounds such as mixed cresols.

Methods are known for preparing the various products which are preparedherein employing the process of the present invention.

U.S. Pat. No. 3,884,981 discloses the use of the oxides of chromium,manganese and nickel in a hydrogenolysis-dehydrogenation of 2-butanol tomethyl ethyl ketone. A two-component feed required is comprised ofsec-butanol plus sec-butyl acetate. U.S. Pat. No. 3,420,887 describesthe conversion of aliphatic alcohols to their corresponding aldehydesand ketones such as 2-butanol to methyl ethyl ketone and 1-butanol to1-butanal using a calcium nickel phosphate catalyst. U.S. Pat. No.3,998,884 employs metallic nickel on an inert support to convert phenolto cyclohexanol and cyclohexanone using controlled amounts of water.

It is of economic and chemical importance, particularly in times ofreactant short supply, to have alternate methods of preparation oralternate catalyst systems that can be used to make the various types ofaldehydes, alcohols and ketones.

It is an object of this invention to convert an alkyl and/or arylhydroxy compound. It is another object of this invention to convert suchcompounds to at least one of an aldehyde, alcohol, and ketone. It is astill further object of the invention to provide an alternate processfor the preparation of known compounds. Another object of the inventionis to provide a catalytic process for the conversion of an alkyl and/oraryl hydroxy compound. A still further object of the invention is toprovide a catalytic process for the conversion of at least one of analkyl and an aryl hydroxy compound to at least one of an aldehyde,alcohol and ketone.

Other aspects, concepts, objects and the several advantages of theinvention are apparent from a study of this disclosure and the appendedclaims.

According to the present invention there is provided a process for theconversion of at least one of an alkyl, an aryl hydroxy compound to auseful product which comprises subjecting at least one of said alkyl andaryl hydroxy compound to the action of hydrogen, under reactionconditions including a catalyst comprising the oxides of manganese,nickel, and magnesium.

The following feedstocks are presently contemplated and are includedwithin the scope of the claimed invention.

ALIPHATIC PRIMARY ALCOHOLS

Materials useful in this invention to prepare aliphatic aldehydes arethose aliphatic primary alcohols represented by the formula ##STR1##wherein R can be any alkyl or cycloalkyl radical having from 1 to 20carbon atoms. For example, materials to be used that correspond toformula I can be, but not limited to

ethanol

1-propanol

1-butanol

2-methyl-1-propanol

2-methyl-1-butanol

3-methyl-1-butanol

2,2-dimethyl-1-propanol

2-methyl-1-pentanol

1-hexanol

1-heptanol

1-dodecanol

and the like and mixtures thereof.

ALIPHATIC SECONDARY ALCOHOLS

Materials useful in this invention to prepare aliphatic ketones arethose aliphatic secondary alcohols represented by the formula ##STR2##wherein each R' can be the same or different and can be any alkyl orcycloalkyl radical having from 1 to 10 carbon atoms. For example,materials to be used that correspond to formula II can be, but notlimited to

2-propanol

2-butanol

2-pentanol

3-pentanol

3-methyl-2-butanol

2-hexanol

3-hexanol

2,2-dimethyl-3-butanol

2-decanol

3-decanol

2-dodecanol

3-dodecanol

and the like, and mixtures thereof.

AROMATIC HYDROXY COMPOUNDS

Materials useful in this invention to prepare cycloaliphatic alcoholsand cycloaliphatic ketones are those aromatic hydroxy compoundsrepresented by the formula ##STR3## wherein R" can be hydrogen or anyalkyl or cycloalkyl radical having from 1 to 6 carbon atoms. Forexample, materials to be used that correspond to formula III can be, butnot limited to

phenol

o-cresol

m-cresol

p-cresol

2,3-xylenol

2,4-xylenol

2,5-xylenol

2,6-xylenol

3,4-xylenol

3,5-xylenol

2,3,4-trimethylphenol

2,3,5-trimethylphenol

2,3,6-trimethylphenol

2,4,6-trimethylphenol

3,4,5-trimethylphenol

2-ethylphenol

2-hexylphenol

2,4-dihexylphenol

2-methyl-4-ethylphenol

2-cyclohexylphenol

and the like and mixtures thereof.

A small amount of water (e.g. 2 wt.%) can be present in the feed but itis not required nor does it appear now to be beneficial in any way.Water is sometimes present in such feeds because of insufficient drying.The invention accomodates well to such water.

The catalyst system of the current invention has been disclosed andclaimed elsewhere.

The method of preparing the catalyst useful in this invention can beconventional and any known method can be used. The essential elements ofthe catalyst are manganese oxide, nickel oxide and magnesium oxidesupplied by impregnation of the latter oxide with an aqueous solution ofmanganese nitrate and nickel nitrate. Alumina, which is known in the artas a nickel oxide activator or promoter can be present with themagnesium oxide. The nickel oxide/manganese oxide/magnesium oxidecatalyst is somewhat brittle with little cohesive strength. The cohesivestrength can be increased by use of a binder. Such a binder can be ablend of fumed silica (Cab-O-Sil^(R)) and water glass (sodium silicateplus water). The hydrated catalyst is dried, preferably under vacuumfollowed by calcining with air or nitrogen or mixtures thereof at 204°C. followed by a subsequent heating at 400° C. for 30 minutes in thepresence of hydrogen. Hydrogen reduces the metal oxide to its lowestpossible valence state while still an oxide. The hydrogen pre-treatmentalso helps to maintain catalyst composition consistency before the feedis introduced. The initial heating or activation of these nitrate typecatalysts should be done outside the reactor because of the nitrous andnitric acid by-products formed during heating that can be harmful to themetal reactor or metal packing. Thereafter, the catalyst can beregenerated in the tubular reactor by passing nitrogen, air, or mixturesthereof over the catalyst at about 200° C. to 400° C.

The amount of manganese oxide present expressed as free manganese can bebroadly 5 to 30 wt. precent of the total catalyst system but it ispreferred to be about 10 to 25 wt. percent.

The amount of nickel oxide present expressed as free nickel can bebroadly 2 to 25 wt. percent of the total catalyst system but it ispreferred to be about 5 to 20 wt. percent. The ratios of nickel oxide tomanganese oxide again expressed as the free metal can be

    ______________________________________                                                          Broadly Preferred                                           ______________________________________                                        nickel/manganese, molar ratio                                                                     0.1/1-3/1 0.2/1-2/1                                       nickel/manganese, wt. ratio                                                                       0.1/1-3/1 0.2/1-2/1                                       ______________________________________                                    

The magnesium oxide employed can be as a pellet to which the aqueousnitrate solutions are mixed and heated or in the form of a water solublehydroxide which is subsequently decomposed to magnesium oxide. Ifpelleted or granulated magnesium oxide is employed it is preferred thatthe particle size be less than 50 mesh as measured by a U.S. Standardsieve screen although any convenient size can be used. The amount ofmagnesium oxide present expressed as free metal can be broadly 50 to 90wt. percent of the total catalyst system but it is preferred to be about60 to 80 wt. percent.

The amount of hydrogen used is expressed as the mole ratio of hydrogento reactant feed (undiluted) and can be broadly from 1:1 to 20:1 butpreferably from 1:1 to about 10:1. Hydrogen can be diluted with inertgases such as nitrogen.

The use of solvents in this invention is optional. The amount of solventused can be about 25 to 75 wt. percent of the total feed. Solventsuseful are the alkanes and cycloalkanes having from about 5 to 7 carbonatoms such as pentane, hexane, heptane, methylcyclopentane, cyclohexane,and the like.

    ______________________________________                                        E. Reaction Conditions                                                                          Broad       Preferred                                       ______________________________________                                        1.  Temperatures                                                                  °F.        400-900     600-800                                         °C.        204-482     315-426                                     2.  Pressures                                                                     psi                50-600      75-500                                         MPa               0.344-4.138 0.517-3.448                                 3.  Flow Rates                                                                    Liquid Hourly Space                                                                             0.1-10      0.5-5.0                                         Velocity (LHSV)                                                           ______________________________________                                    

The following examples serve to illustrate the operability of thisinvention.

EXAMPLE I

This example illustrates the usefulness of the inventive catalyst,MnO/NiO/MgO, in the conversion of a secondary alcohol, 2-butanol, to aketone, methyl ethyl ketone (MEK). The catalyst was prepared as follows:To 30 milliliters of a 50 wt. % aqueous solution (from Mallinckrodt)which contained 23.4 grams of Mn(NO₃)₂ was added 30 milliliters of waterand 9.5 grams of Ni(NO₃)₂.6 H₂ O. The resulting paste was slowly addedto a vigorously stirred solution of 40.9 grams of MgO and 60 millilitersof water. The newly formed thick pasty-like mixture was poured into a15.24 cm. (6 in.)×0.32 cm. (0.125 in.)×0.32 cm. (0.125 in.) rubber mold.At this point, the molar amounts of free metal available was estimatedto be 1.01 moles of Mg; 0.13 moles of Mn; 0.033 moles of Ni. The ratioof active metals is shown below. Since the exact oxide form of the metalis not known, the values are expressed on the basis of free metal.

    ______________________________________                                                  Proportions of Metals                                               Metal Ingredients                                                                         Molar Ratio.sup.a                                                                         Wt. Ratio %.sup.a                                                                         Wt. %                                     ______________________________________                                        Manganese   1.0         1.0         21.2                                      Nickel      0.25        0.27         5.7                                      Magnesium   7.77        3.44        73.1                                      ______________________________________                                         .sup.a Based on 1.0 for manganese                                        

After drying overnight at ambient room temperature, the mold andcatalyst were placed in a vacuum oven (20 mm) at 93° C. (200° F.) for 2hours. The slab of catalyst formed was broken into small pieces andcalcined in a quartz tube with a 50:50 volume percent air and nitrogen,first at 316° C.-371° C. (600° F.-700° F.) to remove oxides of nitrogen,then at 482° C. (900° F.-950° F.). An alternate method of removing waterand nitrogen oxides is to put the catalyst in a vacuum oven (<10 mmpressure) for 16-24 hours at 204° C. (400° F.). Catalyst dried by eithermethod is activated by heating to about 10° C. (50° F.) above thedesired operating temperature while a stream of hydrogen, containingsome nitrogen initially, is passed through the reactor. The mole ratioof active nickel to manganese is estimated to be 0.25/1.0.

To a 316 stainless steel tubular reactor having the dimensions 2.44 cm.(0.960 in.) diameter by 70.49 cm. (27.75 in.) and equipped with anexternal electrical heater and a Moore back-pressure regulator wascharged 60 milliliters of the catalyst described above mixed with about73 milliliters of 316 stainless steel Helipak (0.125 in.×0.125 in.)which was used as a heat transfer agent to help control the temperatureof the reaction which was usually exothermic. While the temperature wasmaintained at about 427° C. (900° F.) and 0.55 MPa (80 psi) H₂ pressure,2-butanol was fed through the reactor at a rate of 40 milliliters perhour (0.665 LHSV), the pressure being maintained by hydrogen which mixeswith the feed at a molar ratio of about 1.0 mole of hydrogen to 1.0 moleof 2-butanol. The effluent product was analyzed without furtherseparation with a Bendix^(R) 2300 chromatograph employing a columnpacked with Porapak (QS) from Waters Inc. This type column separates2-butanol and MEK. The column was programmed as follows: 100° C. to 190°C. at 30° C./min.; 190° C. to 250° C. at 10° C./min.; and isothermal at250° C. until complete. The analysis showed the following products: 0.77wt. % 1-butene; 2.50 wt. % 2-butenes (c & t); 77.28 wt. % MEK; 13.97 wt.% 2-butanol; and 5.48 wt. % heavies. On the basis of the analysis, therewas an 86.1% conversion of 2-butanol with a 89.8% selectivity to MEK.This run was repeated at several different temperatures. These resultswhich are listed below indicate the highest MEK selectivities at about343° C. (650° F.) but the highest 2-butanol conversion at 427° C. (800°F.).

                                      TABLE I                                     __________________________________________________________________________    Conversion of 2-Butanol to Methyl Ethyl Ketone (MEK)                          Using the Catalyst MgO/MnO/NiO and 0.5 MPa (80 psi) Hydrogen Pressure         Reaction                                                                            %                             %                                         Temp. 2-Butanol                                                                           % Area by GLC           MEK                                       °C.                                                                       °F.                                                                       Conversion                                                                          2-Butanol                                                                          1-Butene                                                                           2-Butenes                                                                          MEK Heavies                                                                            Selectivity.sup.a                         __________________________________________________________________________    315                                                                              600                                                                              23.2  76.80                                                                              0.29 0.73 20.74                                                                             1.44 89.4                                      332                                                                              630                                                                              21.4  78.56                                                                              0.19 0.53 20.57                                                                             0.15 95.9                                      343                                                                              650                                                                              24.3  75.72                                                                              0.18 0.56 23.44                                                                             0.10 96.5                                      371                                                                               700.sup.b                                                                       43.9  56.16                                                                              0.30 0.81 40.62                                                                             2.13 92.9                                      398                                                                              750                                                                              62.0  38.04                                                                              0.49 0.87 57.13                                                                             3.47 92.2                                      427                                                                              800                                                                              86.1  13.97                                                                              0.77 2.50 77.28                                                                             5.48 89.8                                      __________________________________________________________________________     .sup.a % Area MEK ÷ Total % Areas = % MEK Selectivity. 2Butanol           considered recyclable.                                                        .sup.b Values result of 2 runs.                                          

EXAMPLE II

This example illustrates the use of a control catalyst, MnO/MgO, withoutNiO. To 29.6 milliliters of a 50 wt. % aqueous solution which contained23.1 grams (0.13 moles) of Mn(NO₃)₂ was added 59.1 grams (1.46 moles) ofMgO (SMR-7-4938 from Grace Chemical Co.) along with 100 milliliters ofwater. The thick mixture was subsequently processed in the same manneras described in Example I.

The reactor experiment described in Example I was repeated using thecatalyst MnO/MgO. These results are listed in Table II and show lowerselectivities to MEK than those obtained at comparable temperatures withthe inventive catalyst system containing NiO (see Table I).

                                      TABLE II                                    __________________________________________________________________________    Conversion of 2-Butanol to Methyl Ethyl Ketone (MEK) Using                    the Catalyst MnO/MgO and 0.5 MPa (80 psi) Hydrogen Pressure                   Reaction                                                                            %                                       %                               Temp.,                                                                              2-Butanol                                                                           % Area by GLC                     MEK                             °C.                                                                       °F.                                                                       Conversion                                                                          2-Butanol                                                                          1-Butene                                                                           2-Butenes                                                                          MEK Aldol 1.sup.a                                                                      Aldol 2.sup.b                                                                      Heavies                                                                            Selectivity                     __________________________________________________________________________    315                                                                              600                                                                              41.7  58.32                                                                              0.15 1.03 30.33                                                                             3.06 5.51 1.60 72.8                            371                                                                              700                                                                              82.6  17.37                                                                              0.68 2.04 63.71                                                                             5.69 4.59 5.90 77.1                            __________________________________________________________________________     .sup.a 1Ethyl-3-methyl-pentenone                                              .sup.b 1,2,3Trimethyl-2-pentenone                                        

EXAMPLE III

This example illustrates the usefulness of the inventive catalyst,MnO/NiO/MgO, in the conversion of a primary alcohol, 2-methyl-1-butanol,to an aldehyde, 2-methyl-1-butanol.

The reactor experiment described in Example I was repeated using thesame catalyst, 1.01 moles Mg/0.13 moles Mn/0.033 moles Ni except thefeed was 2-methyl-1-butanol. The hydrogen pressure was also the same. At315° C. (600° F.), conversion was 34.2% with a 59.4% selectivity to2-methyl-1-butanal. At 427° C. (800° F.), the conversion was 55.3% withan aldehyde selectivity of 92.3%.

In a second series of runs the amount of Ni(NO₃)₂.6 H₂ O used in thecatalyst system was increased from 9.50 grams to 14.25 grams. Thischanged the Ni/Mn mole ratio from 0.25/l to 0.35/l. The increased nickelcontent lowered both the % conversion of 2-methyl-1-butanol and the %selectivity to the corresponding aldehyde. These results are shown inTable III.

                  TABLE III                                                       ______________________________________                                        Conversion of 2-Methyl-1-Butanol to 2-Methyl-1-Butanal                        Using the Catalyst                                                            MnO/NiO/MgO and 0.5 MPa (80 psi) Hydrogen Pressure                                             %                                                            Molar  Reaction  Conversion                                                   Ratio  Temp.     of 2-Methyl-                                                                             2-Methyl-                                                                              2-Methyl-                                of Ni/Mn                                                                             °C.                                                                           °F.                                                                           1-Butanol                                                                              1-&2-Butenes                                                                           1-Butanal                              ______________________________________                                        1/4    315    600    34.2     0.2      59.4                                   1/4    427    800    55.3     0.2      92.3                                   3/8    315    600    22.3     0.6      78.3                                   3/8    371    700    43.3     0.7      89.8                                   3/8    427    800    49.0     1.6      81.3                                   ______________________________________                                    

EXAMPLE IV

This example illustrates the use of a control catalyst, MnO/MgO, withoutNiO. The procedure described in Example II was repeated except the feedwas 2-methyl-1-butanol instead of 2-butanol. These results are listed inTable IV and show much lower 2-methyl-1-butanol conversions than thoseobtained at comparable temperatures with the inventive catalyst systemcontaining NiO (see Table III).

                  TABLE IV                                                        ______________________________________                                        Conversion of 2-Methyl-1-Butanol to 2-Methyl-1-Butanol                        Using the Catalyst                                                            MnO/MgO and 0.5 MPa (80 psi) Hydrogen Pressure                                Reaction % Conversion % Selectivity by GLC                                    Temp.    of 2-Methyl- 2-Methyl-   2-Methyl-                                   °C.                                                                         °F.                                                                            1-Butanol    1&2-Butenes                                                                             1-Butanol                                 ______________________________________                                        315  600      2.9         0.0       95.0                                      371  700     15.8         3.6       94.8                                      427  800     39.0         5.7       83.6                                      ______________________________________                                    

EXAMPLE V

This example illustrates the use of another control wherein the NiOportion of the inventive catalyst system was replaced with CaO. Thecatalyst was prepared in a similar manner as described herein using 90grams (2.23 moles) MgO, 12.6 grams (0.053 moles) of Ca(NO₃)₂.4 H₂ O, and87 grams (0.24 moles) of a 50 wt. percent aqueous solution of Mn(NO₃)₂.The molar ratios of free metal was estimated at 1.0 moles Mg/0.11 molesMn/0.023 moles Ca. The molar ratio of Ca to Mn was also estimated to be1/4.5. The reactor runs described in Example I were repeated except thefeed was 2-methyl-1-butanol and the catalyst was MgO/MnO/CaO. Theseresults which are listed in Table V show very low 2-methyl-1-butanolconversions as compared to those obtained with the inventive catalyst atcomparable temperatures (see Table IV).

                  TABLE V                                                         ______________________________________                                        Conversion of 2-Methyl-1-Butanol to 2-Methyl-1-Butanal                        Using the Catalyst                                                            MnO/MgO/CaO and 0.5 MPa (80 psi) Hydrogen Pressure                            Reaction % Conversion % Selectivity by GLC                                    Temp.    of 2-methyl- 2-Methyl-   2-Methyl-                                   °C.                                                                         °F.                                                                            1-Butanol    1&2-Butenes                                                                             1-Butanal                                 ______________________________________                                        315  600     1.6          0.0       91.6                                      371  700     4.1          3.5       94.1                                      427  800     13.1         4.5       91.3                                      ______________________________________                                    

EXAMPLE VI

This example illustrates the use of another control wherein the catalystemployed, cobalt molybdate on alumina, is also known as an olefindisproportionation catalyst and a hydrodesulfurization catalyst. Theprocedure described in Example III was repeated except the MnO/MgO/NiOwas replaced with a cobalt molybdate on alumina catalyst (F-475-16,Filtrol Corp.). The results shown in Table VI show very high2-methyl-1-butanol conversions but no 2-methyl-1-butanal product.

                  TABLE VI                                                        ______________________________________                                        Conversion of 2-Methyl-1-Butanol to 2-Methyl-1-Butanal                        Using the Catalyst Cobalt Molybdate on Alumina and 0.5 MPa                    (80 psi) Hydrogen Pressure                                                            %                                                                     Reaction                                                                              Conversion                                                                              % Selectivity by GLC                                        Temp.   of 2-Methyl-                                                                            2-Methyl 2-Methyl                                                                              2-Methyl                                                                             Oth-                                °C.                                                                         °F.                                                                           1-Butanol Butene-1                                                                             Butene-2's                                                                            1-Butanal                                                                            ers                               ______________________________________                                        315  600    93.4      29.99  66.05   0      3.96                              371  700    98.3      28.60  65.04   0      6.36                              ______________________________________                                    

EXAMPLE VII

This is a control run using Ca₃ (PO₄)₂ as a catalyst to replace theinventive catalyst MnO/NiO/MgO used in Example III. Ca₃ (PO₄)₃ (N.F.powder from Mallinckrodt) was ground between steel rollers to a granularmaterial of less than 8 mesh size before using. These results listed inTable VII show high aldehyde selectivity at 315° C. but low %conversion. As the temperature was increased, the % butanol conversionwas increased but the aldehyde selectivity decreased.

                  TABLE VII                                                       ______________________________________                                        Conversion of 2-Methyl-1-Butanol to 2-Methyl-1-Butanal                        Using the Catalyst                                                            Ca.sub.3 (PO.sub.4).sub.2 and 0.5 MPa (80 psi) Hydrogen Pressure                      %                                                                     Reaction                                                                              Conversion                                                                              % Selectivity by GLC                                        Temp.   of 2-Methyl-                                                                            2-Methyl 2-Methyl                                                                              2-Methyl-                                                                            Oth-                                °C.                                                                         °F.                                                                           1-Butanol Butene-1                                                                             Butene-2's                                                                            1-Butanal                                                                            ers                               ______________________________________                                        315  600    8.9       12.1    3.5    83.5   0.9                               371  700    27.6      23.4   13.3    61.1   2.2                               398  750    66.7      22.0   28.6    46.5   2.9                               ______________________________________                                    

EXAMPLE VIII

This example illustrates the usefulness of the inventive catalyst,MnO/NiO/MgO, in converting aromatic hydroxy compounds into saturatedring alcohols and ketones. The inventive catalyst was basically the sameas described in Example I except the molar ratio of Ni/Mn was changedfrom 0.25/1.0 to 1.7/1. In addition, a little fumed silica and sodiumsilicate (water glass) was added as a binder. The catalyst was preparedin the same manner as the inventive catalyst in Example I except from asolution containing 1.8 grams (0.004 moles) Al(NO₃)₃.9 H₂ O, 33.0 grams(0.113 moles) Ni(NO₃)₂.6 H₂ O, 11.7 grams (0.065 moles) Mn(NO₃)₂, 60grams water, 59.1 grams (1.01 moles) Mg(OH)₂, 0.5 grams (0.008 moles)fumed SiO₂ (Cab-O-Sil^(R)), and 6 milliliters of water glass (2 grams(0.007 moles) Na₂ SiO₃.9 H₂ O). The ratio of active metals is shownbelow. Since the exact oxide form of the metal is not known, the valuesare expressed on the basis of free metal.

    ______________________________________                                                   Proportions of Metals                                              Metal Ingredients                                                                          Molar Ratio.sup.a                                                                         Wt. Ratio.sup.a                                                                          Wt. %                                     ______________________________________                                        Manganese    1.0         1.0        10.2                                      Nickel       1.7         1.86       18.8                                      Magnesium    15.5        6.86       69.7                                      Aluminum     0.06        0.03        0.3                                      ______________________________________                                         .sup.a Based on 1.0 for manganese.                                       

The reactor run procedure described in Example I was repeated using theabove catalyst and liquid o-cresol as the feed. The data listed in TableVIII shows about equal distribution in selectivity between2-methylcyclohexanol and 2-methylcyclohexanone. Increasing hydrogenpressure favors the formation of 2-methylcyclohexanone.

                                      TABLE VIII                                  __________________________________________________________________________    Conversion of o-Cresol to 2-Methylcyclohexanol and                            2-Methylcyclohexanone Using the Catalyst MnO/NiO/MgO at Various               Hydrogen Pressures                                                            (Temp. 315° C., 600° F.)                                        Reaction    % Selectivity Based on GLC                                        Pressure                                                                            %               Methyl-     Cyclo-   2-Methyl-                                                                             2-Methyl-                  Mpa                                                                              psi                                                                              Conversion                                                                          Benzene                                                                            Toluene                                                                            Cyclohexane                                                                          Xylenols                                                                           hexanol                                                                            Phenol                                                                            Cyclohexanone                                                                         Cyclohexanol.sup.a         __________________________________________________________________________    0.689                                                                            100                                                                              41.0  1.1  --   --     15.3 5.5  13.1                                                                              35.9    29.1                       1.379                                                                            200                                                                              76.5  0.8  0.4  1.0    5.5  7.1  2.5 38.1    43.6                       2.069                                                                            300                                                                              55.1  0.6  0.6  1.0    5.1  4.5  3.7 42.5    41.2                       __________________________________________________________________________

EXAMPLE IX

This example illustrates the usefulness of the inventive catalyst inExample VIII wherein the molar ratio of Ni/Mn is 1.7/1 and the feed washot liquid m-cresol. In addition, another catalyst was used based on theinventive catalyst combination of MnO/NiO/MgO but where the molar ratiowas changed to 0.25/1.0 of Ni/Mn. The data listed in Table IX shows goodselectivity of the cis and trans 3-methylcyclohexanol although %m-cresol conversions are low. Increased hydrogen pressure favors theformation of 3-methylcyclohexanone. When the Ni/Mn is changed from 1.7/1to 0.25/1 there still is some activity but the % m-cresol conversion islowered.

                                      TABLE IX                                    __________________________________________________________________________    Conversion of m-Cresol                                                        (Temp. 315° C., 600° F.)                                               Reaction   % Selectivity Based on GLC                                  Molar Ratio                                                                          Pressure                                                                            %    Cyclo-       3-Methyl-                                                                             3-Methyl-                              of Ni/Mn                                                                             MPa                                                                              psi                                                                              Conversion                                                                         Hexane                                                                            Toluene                                                                            Phenol                                                                            Cyclohexanone                                                                         Cyclohexanol.sup.a                     __________________________________________________________________________    4/1    0.689                                                                            100                                                                               1.6 --  25.4 --  --      74.6                                   4/1    2.758                                                                            400                                                                              26.6 1.2 4.0  1.2 24.5    68.5                                   1/4    0.689                                                                            100                                                                              trace                                                                              --  --   --  --      --                                     1/4    2.758                                                                            400                                                                              15.1 --  2.1  --  34.9    65.1                                   __________________________________________________________________________     .sup.a Includes cis and trans isomers                                    

EXAMPLE X

This example illustrates the use of the inventive composition catalyst,MnO/NiO/MgO, wherein the molar ratio of Ni/Mn was 0.25/1.0 and the feedwas hot liquid p-cresol. The results shown in Table X indicate lowp-cresol conversion (25.9%) with the major product being4-methylcyclohexanol.

                  TABLE X                                                         ______________________________________                                        Conversion of p-Cresol                                                        (Temp. 315° C., 600° F.)                                        Reaction Pressure                                                                        %          4-Methyl-  4-Methyl-                                    MPa   psi      Conversion Cyclohexanone                                                                          Cyclohexanol.sup.a                         ______________________________________                                        0.689 100      trace      --       --                                         2.758 400      25.9       74.4     22.1                                       ______________________________________                                         .sup.a Includes cis and trans isomers.                                   

The data herein disclosed is summarized in Table XI wherein it is seenthe advantage of using the catalyst system MnO/NiO/MgO in the presenceof hydrogen to convert secondary paraffinic alcohols to ketones, primaryparaffinic alcohols to aldehydes and aromatic hydroxy compounds tocycloaliphatic alcohols and ketones. The metals considered mostessential, Ni and Mn, as their oxides can function in molar ratiosexpressed as free metals varying from 0.25/1 to 1.7/1. With paraffinicalcohols the 0.25/1 Ni/Mn molar ratio works well but with aromatichydroxy compounds a 1.7/1 Ni/Mn molar ratio works best.

It is evident from the foregoing that the process of the inventionprovides alternate and improved operation when considered in light ofthe prior art.

                                      TABLE XI                                    __________________________________________________________________________    Summary of MnO/NiO/MgO Catalyzed Reactions                                    on Paraffinic and Aromatic Hydroxy Compounds                                  __________________________________________________________________________                   Approx.                                                                       Molar                                                                         Ratio                   % Feed                                                                              Principal   % Product            Example                                                                             Catalyst Ni/Mn Reaction Temp., °C.                                                                Feed  Conversion                                                                          Product(s)  Selectivity          __________________________________________________________________________    I     MnO/NiO/MgO                                                                            0.25/1                                                                              371         2-Butanol                                                                           43.9  Methyl Ethyl                                                                              92.9ne               I     MnO/NiO/MgO                                                                            .25/1 427         2-Butanol                                                                           86.1  Methyl Ethyl                                                                              89.8ne               II    MnO/MgO  .25/1 371         2-Butanol                                                                           41.7  Methyl Ethyl                                                                              72.8ne               II    MnO/MgO  .25/1 427         2-Butanol                                                                           82.6  Methyl Ethyl                                                                              77.1ne               III   MnO/NiO/MgO                                                                            .25/1 427         2-Methyl-1-                                                                         55.3  2-Methyl-1-butanal                                                                        92.3                                                  butanol                                      III   MnO/NiO/MgO                                                                            .35/1 371         2-Methyl-1-                                                                         43.3  2-Methyl-1-butanal                                                                        89.8                                                  butanol                                      III   MnO/NiO/MgO                                                                            .35/1 427         2-Methyl-1-                                                                         49.0  2-Methyl-1-butanal                                                                        81.3                                                  butanol                                      IV    MnO/MgO  --    371         2-Methyl-1-                                                                         15.8  2-Methyl-1-butanal                                                                        94.8                                                  butanol                                      IV    MnO/MgO  --    427         2-Methyl-1-                                                                         39.0  2-Methyl-1-butanal                                                                        83.6                                                  butanol                                      V     MnO/CaO/MgO                                                                            --    371         2-Methyl-1-                                                                         4.1   2-Methyl-1-butanal                                                                        94.1                                                  butanol                                      V     MnO/CaO/MgO                                                                            --    427         2-Methyl-1-                                                                         13.1  2-Methyl-1-butanal                                                                        91.3                                                  butanol                                      VI    Cobalt Molyb-                                                                          --    371         2-Methyl-1-                                                                         98.3  2-Methyl-1-butanal                                                                        0                          date/Al.sub.2 O.sub.3      butanol                                      VII   Ca.sub.3 (PO.sub.4).sub.3                                                              --    371         2-Methyl-1-                                                                         27.6  2-Methyl-1-butanal                                                                        61.1                                                  butanol                                      __________________________________________________________________________                   Approx.                                                                       Molar                                                                         Ratio                   % Feed                                                                              Principal   % Product            Example                                                                             Catalyst Ni/Mn Temp., °C.                                                                   H.sub.2 Press.                                                                      Feed  Conversion                                                                          Product(s)  Selectivity          __________________________________________________________________________    VIII  MnO/NiO/MgO.sup.a                                                                      1.7/1 375   100 psi                                                                             o-cresol                                                                            41.0  2-Methylcyclohexanone                                                                     29.1                                                              2-Methylcyclohexanol                                                                      35.9                 VIII  MnO/NiO/MgO.sup.a                                                                      1.7/1 315   200 psi                                                                             o-cresol                                                                            76.5  2-Methylcyclohexanone                                                                     38.1                                                              2-Methylcyclohexanol                                                                      43.6                 VIII  MnO/NiO/MgO.sup.a                                                                      1.7/1 315   300 psi                                                                             o-cresol                                                                            55.1  2-Methylcyclohexanone                                                                     42.5                                                              2-Methylcyclohexanol                                                                      41.2                 IX    MnO/NiO/MgO                                                                            1.7/1 315   100 psi                                                                             m-cresol                                                                            0                                      IX    MnO/NiO/MgO                                                                            1.7/1 315   400 psi                                                                             m-cresol                                                                            15.1  3-Methylcyclohexanone                                                                     34.9                                                              3-Methylcyclohexanol                                                                      65.1                 IX    MnO/NiO/MgO                                                                            .25/1 315   100 psi                                                                             m-cresol                                                                            1.6   3-Methylcyclohexanone                                                                     0                                                                 3-Methylcyclohexanol                                                                      74.6                 IX    MnO/NiO/MgO                                                                            4/1   315   400 psi                                                                             m-cresol                                                                            26.6  3-Methylcyclohexanone                                                                     24.5                                                              3-Methylcyclohexanol                                                                      68.5                 X     MnO/NiO/MgO                                                                            1/4   315   100 psi                                                                             p-cresol                                                                            0     4-Methylcyclohexanone                                                                     74.4                 X     MnO/NiO/MgO                                                                            1/4   315   400 psi                                                                             p-cresol                                                                            25.9  4-Methylcyclohexanol                                                                      22.1                 __________________________________________________________________________     Also contains <1 wt. % alumina and a binder based on fumed silica and         sodium silicate (water glass).                                           

Reasonable variation and modification are possible within the scope ofthe foregoing disclosure and the appended claims to the invention theessence of which is that at least one of an alkyl and an aryl hydroxylcompound is converted under dehydrogenation conditions in the presenceof hydrogen and a catalyst comprised of the oxides of manganese, nickeland magnesium as herein described; and at good selectivities todesirable products are obtainable, also as herein described.

I claim:
 1. A process for the dehydrogenation of at least one compoundselected from the group consisting of alkyl and cycloalkyl hydroxycompounds, on the hydrogenation of an aryl hydroxy compound, whichcomprises subjecting said compound to the action of hydrogen underdehydrogenation conditions or hydrogenation conditions, respectively, inthe presence of a catalyst comprising the oxides of manganese, nickeland magnesium, wherein the amounts of the oxides, expressed as freemetals present, are 5-30, wt. % manganese, 2-25 wt. % nickel, and 50-90wt. % magnesium.
 2. A process according to claim 1 wherein the alkyl orcycloalkyl hydroxy compound is at least one of a primary alcohol and asecondary alcohol, the primary alcohol is represented by the formula##STR4## wherein R is selected from alkyl and cycloalkyl radicals having1 to 20 carbon atoms, the secondary alcohol is represented by theformula ##STR5## wherein each R' is selected from alkyl and cycloalkylradicals having from 1 to 10 carbon atoms, and wherein the aryl hydroxycompound is represented by the formula ##STR6## wherein each R" isselected from hydrogen, alkyl and cycloalkyl radicals having from 1 to 6carbon atoms.
 3. A process according to claim 2 wherein the primaryalcohol is at least one selected from the group consisting ofethanol1-propanol 1-butanol 2-methyl-1-propanol 2-methyl-1-butanol3-methyl-1-butanol 2,2-dimethyl-1-propanol 2-methyl-1-pentanol 1-hexanol1-heptanol and 1-dodecanol,wherein the secondary alcohol is at least oneselected from the group consisting of 2-propanol 2-butanol 2-pentanol3-pentanol 3-methyl-2-butanol 2-hexanol 3-hexanol 2,2-dimethyl-3-butanol2-decanol 3-decanol 2-dodecanol and 3-dodecanol,and wherein the arylhydroxy compounds is at least one selected from the group consisting ofphenol o-cresol m-cresol p-cresol 2,3-xylenol 2,4-xylenol 2,5-xylenol2,6-xylenol 3,4-xylenol 3,5-xylenol 2,3,4-trimethylphenol2,3,5-trimethylphenol 2,3,6-trimethylphenol 2,4,6-trimethylphenol3,4,5-trimethylphenol 2-ethylphenol 2-hexylphenol 2,4-dihexylphenol2-methyl-4-ethylphenol and 2-cyclohexylphenol.
 4. A process according toclaim 1 wherein the respective weights percent are as follows: 10-25;5-20; and 60-80.
 5. A process according to claim 2 wherein2-methyl-1-butanol is selected as the alkyl hydroxy compound and it isconverted to 2-methyl-1-butanal.
 6. A process according to claim 2wherein the alkyl hydroxy compound selected is 2-butanol and it isconverted to methyl ethyl ketone.
 7. A process according to claim 2wherein orthocresol is the aryl hydroxy compound selected and it isconverted to 2-methylcyclohexanol and 2-methylcyclohexanone.
 8. Aprocess according to claim 2 wherein the aryl hydroxy compound selectedis m-cresol and it is converted to cis- and trans-methylcyclohexanol. 9.A process according to claim 2 wherein the aryl hydroxy compoundselected is p-cresol and it is converted to 4-methylcyclohexanol.
 10. Aprocess according to claim 1 wherein the molar ratio of nickel tomanganese, expressed as the free metal, is in the range 0.1/1-3/1.
 11. Aprocess according to claim 1 wherein the nickel/manganese the molarratio, expressed as the free metal, is in the range 0.2/-2/1.
 12. Aprocess according to claim 1 wherein the operating conditions include atemperature in the approximate range 400°-900° F. and the amount ofhydrogen expressed as the mole ratio hydrogen to reactant feed is in theapproximate range 1:1 to 20:1 and the pressure is in the approximaterange 50-600 psi.